EP3763842B1 - Composite material made of gold - Google Patents

Composite material made of gold Download PDF

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Publication number
EP3763842B1
EP3763842B1 EP19185638.4A EP19185638A EP3763842B1 EP 3763842 B1 EP3763842 B1 EP 3763842B1 EP 19185638 A EP19185638 A EP 19185638A EP 3763842 B1 EP3763842 B1 EP 3763842B1
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EP
European Patent Office
Prior art keywords
composite composition
advantageously
composite
epoxy resin
particles
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Application number
EP19185638.4A
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German (de)
French (fr)
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EP3763842A1 (en
Inventor
Mickael CHABART
Lucie LE BRIS
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Richemont International SA
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Richemont International SA
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Priority to EP19185638.4A priority Critical patent/EP3763842B1/en
Publication of EP3763842A1 publication Critical patent/EP3763842A1/en
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C5/00—Alloys based on noble metals
    • C22C5/02—Alloys based on gold
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
    • C22C32/0047—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with carbides, nitrides, borides or silicides as the main non-metallic constituents
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
    • C22C32/0094—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with organic materials as the main non-metallic constituent, e.g. resin
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C47/00—Making alloys containing metallic or non-metallic fibres or filaments
    • C22C47/14—Making alloys containing metallic or non-metallic fibres or filaments by powder metallurgy, i.e. by processing mixtures of metal powder and fibres or filaments
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C49/00—Alloys containing metallic or non-metallic fibres or filaments
    • C22C49/02—Alloys containing metallic or non-metallic fibres or filaments characterised by the matrix material
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C49/00—Alloys containing metallic or non-metallic fibres or filaments
    • C22C49/14—Alloys containing metallic or non-metallic fibres or filaments characterised by the fibres or filaments
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
    • B22F2998/10—Processes characterised by the sequence of their steps

Definitions

  • the present invention relates to a composite composition and a composite material based on gold comprising conductive fillers, epoxy and fibers.
  • the field of use of the present invention relates in particular to the manufacture of timepieces, jewelery or jewellery.
  • Composites based on precious metals are commonly used in fields such as watchmaking or jewelry.
  • the properties sought may vary but are generally aesthetic and mechanical.
  • the document US 4,282,174 describes a material comprising metal particles and a thermoplastic polymer of the polyethylene, polystyrene, polymethyl methacrylate or nylon type.
  • a thermoplastic polymer of the polyethylene, polystyrene, polymethyl methacrylate or nylon type The presence of the thermoplastic polymer makes it possible to reduce the density of the composite material. In addition, this material has the advantage of being easily glued.
  • the document EP 2 668 305 discloses a material comprising 3-300 nm metal particles dispersed in an elastomeric silicone resin. Due to its shine and luster properties, this material is used in jewelry in particular.
  • EP 1 918 047 describes the preparation of a material comprising a metal and a thermoplastic polymer, by passage through an extruder. This treatment makes it possible to obtain a homogeneous material having elastic properties.
  • WO 2011/035446 describes a composite material comprising metal nanoparticles of core/shell type and a matrix formed by a polymer loaded with silicate or silica.
  • the purpose of the shell, or coating, of the nanoparticles is to prevent the reaction of the nanoparticles with the matrix during its polymerization.
  • This material has properties of hardness and mechanical resistance.
  • the document WO 2012/119647 describes a material comprising a precious metal and a boron-based ceramic matrix. This type of material has advantages, particularly in terms of hardness and electrical conduction. However, the ceramic matrix remains expensive and delicate to implement. Indeed, this material is prepared by infiltration of the metal at a pressure of 10 to 200 bars.
  • the Applicant has developed a composite material mainly based on gold, relatively light and not requiring a complex preparation process.
  • the present invention relates to a composite material comprising gold particles and an epoxy polymer matrix.
  • This material is electrically conductive, which makes it suitable for plating treatment and/or galvanic surface treatment.
  • the composite composition consists of these four types of components and a hardener. A person skilled in the art will know how to adjust the percentages by weight of the various constituents to reach 100%.
  • the particles may in particular be in the form of flakes or three-dimensional particles, for example spherical particles.
  • the size of the particles corresponds to the largest dimension of the particles, for example the diameter for spherical particles or the length for parallelepipedal or cylindrical or oval particles.
  • epoxy resin hardens by polymerization of monomers and/or prepolymers and/or by crosslinking. After hardening (curing) in the presence of a hardener, it provides hardness properties to the composite material.
  • the composite composition In the absence of hardener, the composite composition is in the form of a paste.
  • the percentages are expressed by weight relative to the weight of the composite composition, advantageously relative to the weight of the composite material, that is to say of the composite composition consisting of the four components above (particles of gold , titanium nitride, epoxy resin, fibers) and a hardener.
  • the dimensions (for example the size or the specific surface) of the particles can be measured according to the conventional techniques used by those skilled in the art, for example by laser granulometry (malvern).
  • the form factor can be determined, the density can also be determined as well as the specific surface by gas pycnometer or by BET, a technology based on Brunauer, Emmett and Teller theory.
  • Grain morphology can be determined by SEM (scanning electron microscopy) and chemical composition by EDX (energy dispersive spectrometry).
  • the gold particles represent at least 75% by weight of the composite composition, advantageously between 75% and 92%.
  • a composite composition or a composite material comprising 75% by weight of gold corresponds to an 18 carat composite.
  • a composite composition or a composite material comprising 92% by weight of gold corresponds to a 22 carat composite.
  • the percentages of the constituents are expressed, without distinction, relative to the weight of the composite composition or of the composite material. However, they advantageously correspond to the percentages of the constituents in the composite material.
  • the gold particles correspond to chemically pure gold particles, i.e. 24 carats. They are advantageously in the form of flakes or spherical particles or oval particles. They can in particular be obtained by chemical reduction of a gold salt or by atomization.
  • Gold flakes correspond to essentially two-dimensional gold particles.
  • the gold particles have a micrometric particle size.
  • the gold particles advantageously the powders of gold flakes, have a specific surface advantageously comprised between 0.22 m 2 /g and 0.35 m 2 /g, more advantageously between 0.26 m 2 /g and 0 .28 m 2 /g.
  • the particles advantageously spherical or parallelepipedal or cylindrical or oval, have an average size advantageously comprised between 1 ⁇ m and 60 ⁇ m, more advantageously between 1 ⁇ m and 50 ⁇ m.
  • size is meant the largest dimension of the particles, the length for oval particles or the diameter for spherical particles.
  • the flakes have an average size advantageously less than or equal to 650 micrometers ( ⁇ 650 ⁇ m), more advantageously between 1 micrometer and 3 micrometers.
  • ⁇ 650 ⁇ m micrometers
  • the size distribution of the gold particles is advantageously relatively narrow.
  • the particle size varies by less than 25%, preferably less than 15%, more preferably less than 10%, relative to the average particle size. These percentages correspond to the maximum difference in size between the largest particles and the smallest particles of gold in the composite composition.
  • the spherical gold particles have a distribution d50 equal to 21.34 ⁇ m and d90 equal to 34.48 ⁇ m.
  • 50%, by weight, of the spherical particles therefore have a size of less than 21.34 ⁇ m while 90%, by weight, of the spherical particles have a size of less than 34.48 ⁇ m.
  • the use of particles having a size of less than 600 nm generates a powder having too large a specific surface, which requires the addition of a larger quantity of resin to maintain a flowability allowing the shaping of the composite composition.
  • particles with a size of less than 600 nm do not make it possible to obtain a composite composition containing at least 75% by weight of gold particles and having satisfactory properties. This results in mechanical properties of the composite material that are markedly lower than those of the composite material according to the invention.
  • Gold particles having a size greater than 600 nm, in particular in the form of gold flakes have the advantage of allowing percolation of gold particles and therefore electrical conduction. This is in particular due to the form factor of the particles which, when it increases, causes the reduction of the percolation threshold and therefore a reduction in the quantity of particles required. This phenomenon is even more present when the gold particles are in the form of flakes, due to their flat shape and narrow size distribution.
  • Titanium Nitride (TiN) particles are electrically conductive fillers.
  • a portion of the gold powder can be replaced by titanium nitride powder in order to have, in the final composition, a proportion of gold greater than or equal to 75% by mass of gold and in order to keep the electrical conductivity of the material thus formed.
  • a proportion of 90% by mass of gold in the final material could be necessary for it to be electrically conductive.
  • Titanium nitride has the advantage of having a golden color, identical or close to that of gold. Titanium nitride powder, on the other hand, has a slightly greener color than gold powder. Also, titanium nitride is a ceramic. As such, titanium nitride provides hardness properties to the composite material, while having a low density, of the order of 5.24 g.cm ⁇ 3 .
  • the titanium nitride particles can advantageously be in powder form.
  • Their average size is advantageously between 0.10 ⁇ m and 3.00 ⁇ m, more advantageously between 1.00 ⁇ m and 3.00 ⁇ m.
  • the size of a particle corresponds to the most important dimension of the section of a particle (sectional view), for example the diameter for spherical particles.
  • the epoxy resin hardens by polymerization of monomers and/or prepolymers and/or by crosslinking in the presence of a hardener.
  • epoxy resin is colorless after curing. In other words, it does not modify the color of the gold particles.
  • the epoxy resin is advantageously poly(bisphenol A-co-epichlorohydrin), more advantageously the chemical compound having CAS number 25068-38-6.
  • the epoxy resin is advantageously crosslinked poly(bisphenol A-co-epichlorohydrin).
  • the epoxy resin may in particular correspond to a formulation marketed under the name Super Sap® CCR Epoxy Resin (from Entropy Resin), EPIKOTE TM Resin MGS LR 385 (from Hexion) or EPIKOTE TM Resin MGS L 235 (from Hexion).
  • the fibers are fibers made of an electrically conductive material, more advantageously carbon fibers, in particular carbon microfibers.
  • the carbon fibers are compatible with the various constituents of the composite material, they are easily integrated within the composite composition or the composite material.
  • the fibers represent between 0.5% and 6.0% by weight of the composite composition (or composite material), more preferably 1.0% and 4.0% by weight.
  • They have an average length advantageously between 100 micrometers and 500 micrometers, more advantageously between 200 micrometers and 250 micrometers.
  • the fibers have an average length of the order of 220 micrometers.
  • the composite composition can also comprise a hardener.
  • the composite material has a ratio, by weight, epoxy resin/hardener advantageously comprised between 100/30 and 100/50, more advantageously between 100/35 and 100/43.
  • the hardener may be a polyamine, advantageously a diamine, preferably polyoxypropylenediamine, advantageously the chemical compound having CAS number 9046-10-0.
  • the hardener may in particular correspond to a formulation marketed under the name Super Sap ® CCS Hardener (from Entropy Resin), Super Sap ® CCF Hardener (from Entropy Resin), EPIKURE TM MGS LH 385 (from Hexion), EPIKURE TM MGS LH 386 (from Hexion) or EPIKURE TM MGS LH 238 (from Hexion).
  • the composite material according to the invention is homogeneous. In other words, its components are evenly distributed within the composite material. Thus, the composite material does not include a concentration gradient of its components. It has a density advantageously between 4.00 g.cm -3 and 7.00 g.cm -3 , more advantageously between 5.00 g.cm -3 and 6.00 g.cm -3 ; the density of gold being equal to 19.30 g.cm -3 .
  • the composite material is in the form of a solid. As already indicated, it comprises a polymer matrix formed by the epoxy resin and the hardener, that is to say a three-dimensional network resulting from the polymerization and/or the crosslinking of the epoxy resin in the presence of the hardener.
  • the composite material advantageously consists of gold particles, titanium nitride particles, fibers and the polymer matrix formed by the epoxy resin and by the hardener. More specifically, the various constituents of the composite material are distributed homogeneously within the polymer matrix.
  • It can be in the form of a finished object or a preform. Thus, when it has been shaped prior to the hardening of the resin, it is a finished article. It can also be in the form of a preform which can be machined, for example a cylinder or a parallelepiped, in particular a block.
  • the composite material according to the invention is electrically conductive.
  • step a) without hardener
  • step b) with hardener
  • steps a) and b) can be carried out by simultaneous addition of all the components of the composite material.
  • the composite composition resulting from step a) is generally in the form of a paste.
  • this composite composition can be homogenized by passing it through a mill, advantageously a three-roll mill, also called a three-roll mill.
  • the formation of the composite composition, with or without a hardener, generally causes the incorporation of air bubbles into the paste.
  • the method can comprise a gas elimination step.
  • This step can advantageously be carried out using a centrifuge or a planetary centrifuge/mixer with a partial vacuum. It can be carried out before step b) and/or before step c) and/or simultaneously with step c).
  • step a) and/or b) The preparation of the composite composition (step a) and/or b)) and any treatments (homogenization and elimination of air) are advantageously carried out at a temperature of between 20°C and 25°C. However, the temperature may vary from step to step.
  • Step b) consists in introducing at least one epoxy resin hardener. As already indicated, this hardener allows the polymerization and/or crosslinking of the epoxy resin.
  • the composite composition can be homogenized by a propeller mixer or passage through a mill, advantageously a three-roll mill also called a three-roll mill.
  • step b) Once the composite composition of step b) has been obtained, it can be shaped.
  • the shaping is carried out according to conventional techniques, for example in a mould. It may be a mold making it possible to obtain a finished article or a preform which will subsequently be machined.
  • the mold is placed in a centrifuge, thus simultaneously ensuring the elimination of air and the shaping of the composite material.
  • the centrifugation is advantageously carried out at a temperature between 20°C and 50°C, more advantageously between 25°C and 35°C.
  • the increase in temperature makes it possible to fluidify the composite composition and accelerates the hardening of the epoxy resin.
  • the composite composition can be centrifuged before and/or after step b), that is to say before and/or after the addition of the hardener.
  • Hardening is, at least partially, carried out simultaneously with shaping. Indeed, a pre-hardening can be carried out during shaping. Pre-curing allows manipulation and completion of the curing of the composite material outside the shaping mold.
  • Another method consists in using a planetary mixer, advantageously with a partial vacuum to degas the composite composition which is in the form of a paste.
  • the hardening corresponds to the formation of a matrix polymer by reaction between the epoxy resin and the hardener.
  • step c) The hardening of step c) is advantageously carried out at a temperature between 20°C and 30°C, more advantageously between 25°C and 30°C. Under these conditions, the titanium nitride particles are not ceramized.
  • the present invention also relates to a shaped composite material or a preform that can be machined before forming a finished object.
  • It also relates to an article of watchmaking, jewelery or jewelery comprising the composite material having been hardened. It can be bracelets, earrings, pendants, necklaces, brooches, tie pins, hairpins, belt buckles, buttons, cufflinks, buckles belts, watch cases...
  • the gold particles are flakes having an average size of the order of 5.5 ⁇ m.
  • the titanium nitride particles have an average size between 0.10 micrometers and 3.00 micrometers.
  • the micro carbon fibers have an average length between 100 micrometers and 500 micrometers.
  • Table 1 summarizes the data relating to this composite material, the theoretical density of which is 5.5 g.cm -3 .
  • Table 1 composite material according to the invention gold glitter titanium nitride Carbon microfibers Epoxy resin + hardener Density (g.cm -3 ) 19.30 5.24 2.25 1.15 Percentage by weight 75.00 8.45 4.00 12.55 Volume percentage 21.36 8.87 9.77 60.00
  • This material being electrically conductive, it can then be covered with a plating.

Description

DOMAINE DE L'INVENTIONFIELD OF THE INVENTION

La présente invention concerne une composition composite et un matériau composite à base d'or comprenant des charges conductrices, de l'époxy et des fibres.The present invention relates to a composite composition and a composite material based on gold comprising conductive fillers, epoxy and fibers.

Le domaine d'utilisation de la présente invention concerne notamment la fabrication d'articles d'horlogerie, de bijouterie ou de joaillerie.The field of use of the present invention relates in particular to the manufacture of timepieces, jewelery or jewellery.

ETAT ANTERIEUR DE LA TECHNIQUEPRIOR STATE OF THE TECHNIQUE

Les composites à base de métaux précieux sont couramment utilisés dans les domaines tels que l'horlogerie ou la bijouterie. Les propriétés recherchées peuvent varier mais elles sont généralement esthétiques et mécaniques.Composites based on precious metals are commonly used in fields such as watchmaking or jewelry. The properties sought may vary but are generally aesthetic and mechanical.

A titre d'exemple, le document US 4,282,174 décrit un matériau comprenant des particules métalliques et un polymère thermoplastique de type polyéthylène, polystyrène, polyméthyl méthacrylate ou nylon. La présence du polymère thermoplastique permet de diminuer la masse volumique du matériau composite. En outre, ce matériau présente l'avantage de pouvoir être facilement collé.For example, the document US 4,282,174 describes a material comprising metal particles and a thermoplastic polymer of the polyethylene, polystyrene, polymethyl methacrylate or nylon type. The presence of the thermoplastic polymer makes it possible to reduce the density of the composite material. In addition, this material has the advantage of being easily glued.

Le document EP 2 668 305 divulgue un matériau comprenant des particules métalliques de 3 à 300 nm dispersées dans une résine silicone élastomère. En raison de ses propriétés de brillance et de lustre, ce matériau est utilisé dans la bijouterie notamment.The document EP 2 668 305 discloses a material comprising 3-300 nm metal particles dispersed in an elastomeric silicone resin. Due to its shine and luster properties, this material is used in jewelry in particular.

Le document EP 1 918 047 décrit la préparation d'un matériau comprenant un métal et un polymère thermoplastique, par passage dans une extrudeuse. Ce traitement permet d'obtenir un matériau homogène ayant des propriétés élastiques.The document EP 1 918 047 describes the preparation of a material comprising a metal and a thermoplastic polymer, by passage through an extruder. This treatment makes it possible to obtain a homogeneous material having elastic properties.

Le document WO 2011/035446 décrit un matériau composite comprenant des nanoparticules métalliques de type coeur/coquille et une matrice formée par un polymère chargé en silicate ou en silice. La coquille, ou enrobage, des nanoparticules a pour but d'empêcher la réaction des nanoparticules avec la matrice lors de sa polymérisation. Ce matériau présente des propriétés de dureté et de résistance mécanique.The document WO 2011/035446 describes a composite material comprising metal nanoparticles of core/shell type and a matrix formed by a polymer loaded with silicate or silica. The purpose of the shell, or coating, of the nanoparticles is to prevent the reaction of the nanoparticles with the matrix during its polymerization. This material has properties of hardness and mechanical resistance.

Le document WO 2012/119647 décrit un matériau comprenant un métal précieux et une matrice céramique à base de bore. Ce type de matériau présente des avantages, notamment en termes de dureté et de conduction électrique. Cependant, la matrice en céramique reste couteuse et délicate à mettre en œuvre. En effet, ce matériau est préparé par infiltration du métal à une pression de 10 à 200 bars.The document WO 2012/119647 describes a material comprising a precious metal and a boron-based ceramic matrix. This type of material has advantages, particularly in terms of hardness and electrical conduction. However, the ceramic matrix remains expensive and delicate to implement. Indeed, this material is prepared by infiltration of the metal at a pressure of 10 to 200 bars.

Afin de remédier aux écueils de l'art antérieur et notamment les difficultés de mise en oeuvre, le Demandeur a mis au point un matériau composite majoritairement à base d'or, relativement léger et ne nécessitant pas de procédé de préparation complexe.In order to remedy the pitfalls of the prior art and in particular the difficulties of implementation, the Applicant has developed a composite material mainly based on gold, relatively light and not requiring a complex preparation process.

EXPOSE DE L'INVENTIONDISCLOSURE OF THE INVENTION

La présente invention concerne un matériau composite comprenant des particules d'or et une matrice polymère époxy. Ce matériau est conducteur électriquement, ce qui le rend adéquat pour un traitement de plaquage et/ou un traitement galvanique en surface.The present invention relates to a composite material comprising gold particles and an epoxy polymer matrix. This material is electrically conductive, which makes it suitable for plating treatment and/or galvanic surface treatment.

La présente invention concerne également la composition composite permettant de préparer ce matériau composite. Cette composition composite comprend, en poids par rapport au poids de la composition composite :

  • au moins 75,00 % de particules d'or,
  • 2% à 10% des particules de nitrure de titane,
  • 5% à 15% une résine époxy,
  • 0,5% à 6,0% des fibres,
les particules d'or ayant une taille supérieure à 600 nm (> 600 nm).The present invention also relates to the composite composition making it possible to prepare this composite material. This composite composition comprises, by weight relative to the weight of the composite composition:
  • at least 75.00% gold particles,
  • 2% to 10% titanium nitride particles,
  • 5% to 15% an epoxy resin,
  • 0.5% to 6.0% fiber,
gold particles having a size greater than 600 nm (> 600 nm).

La composition composite est constituée de ces quatre types de composants et d'un durcisseur. L'homme du métier saura ajuster les pourcentages en poids des différents constituants pour atteindre 100 %.The composite composition consists of these four types of components and a hardener. A person skilled in the art will know how to adjust the percentages by weight of the various constituents to reach 100%.

Les particules (notamment Au et TiN) peuvent notamment se présenter sous la forme de paillettes ou de particules tridimensionnelles, par exemple des particules sphériques. La taille des particules correspond à la dimension la plus importante des particules, par exemple le diamètre pour des particules sphériques ou la longueur pour les particules parallélépipédiques ou cylindriques ou ovales.The particles (in particular Au and TiN) may in particular be in the form of flakes or three-dimensional particles, for example spherical particles. The size of the particles corresponds to the largest dimension of the particles, for example the diameter for spherical particles or the length for parallelepipedal or cylindrical or oval particles.

De manière générale, la résine époxy durcit par polymérisation de monomères et/ou de pré-polymères et/ou par réticulation. Après durcissement (curing) en présence d'un durcisseur, elle apporte des propriétés de dureté au matériau composite.In general, epoxy resin hardens by polymerization of monomers and/or prepolymers and/or by crosslinking. After hardening (curing) in the presence of a hardener, it provides hardness properties to the composite material.

En l'absence de durcisseur, la composition composite se présente sous la forme d'une pâte.In the absence of hardener, the composite composition is in the form of a paste.

Sauf indication contraire, les pourcentages sont exprimés en poids par rapport au poids de la composition composite, avantageusement par rapport au poids du matériau composite c'est-à-dire de la composition composite constituée des quatre composants ci-dessus (particules d'or, nitrure de titane, résine époxy, fibres) et d'un durcisseur.Unless otherwise indicated, the percentages are expressed by weight relative to the weight of the composite composition, advantageously relative to the weight of the composite material, that is to say of the composite composition consisting of the four components above (particles of gold , titanium nitride, epoxy resin, fibers) and a hardener.

De manière générale, les dimensions (par exemple la taille ou la surface spécifique) des particules peuvent être mesurées selon les techniques conventionnelles utilisées par l'homme du métier, par exemple par granulométrie laser (malvern). Avec un système optique adapté, le facteur de forme peut être déterminé, la densité peut également être déterminée ainsi que la surface spécifique par pycnomètre à gaz ou par BET, technologie basée sur la théorie Brunauer, Emmett et Teller. La morphologie des grains peut être déterminée par MEB (microscopie électronique à balayage) et la composition chimique par EDX (spectrométrie à dispersion d'énergie).In general, the dimensions (for example the size or the specific surface) of the particles can be measured according to the conventional techniques used by those skilled in the art, for example by laser granulometry (malvern). With a suitable optical system, the form factor can be determined, the density can also be determined as well as the specific surface by gas pycnometer or by BET, a technology based on Brunauer, Emmett and Teller theory. Grain morphology can be determined by SEM (scanning electron microscopy) and chemical composition by EDX (energy dispersive spectrometry).

Particules d'orgold particles

Les particules d'or représentent au moins 75 % en poids de la composition composite, avantageusement entre 75 % et 92 %. A titre d'exemple, une composition composite ou un matériau composite comprenant 75 % en poids d'or correspond à un composite à 18 carats. Une composition composite ou un matériau composite comprenant 92 % en poids d'or correspond à un composite à 22 carats.The gold particles represent at least 75% by weight of the composite composition, advantageously between 75% and 92%. By way of example, a composite composition or a composite material comprising 75% by weight of gold corresponds to an 18 carat composite. A composite composition or a composite material comprising 92% by weight of gold corresponds to a 22 carat composite.

Comme déjà indiqué, les pourcentages des constituants sont exprimés, sans distinction, par rapport au poids de la composition composite ou du matériau composite. Toutefois, ils correspondent avantageusement aux pourcentages des constituants dans le matériau composite.As already indicated, the percentages of the constituents are expressed, without distinction, relative to the weight of the composite composition or of the composite material. However, they advantageously correspond to the percentages of the constituents in the composite material.

Les particules d'or correspondent à des particules d'or chimiquement pur soit 24 carats. Elles se présentent avantageusement sous la forme de paillettes (flakes) ou de particules sphériques ou de particules ovales. Elles peuvent notamment être obtenues par réduction chimique d'un sel d'or ou par atomisation.The gold particles correspond to chemically pure gold particles, i.e. 24 carats. They are advantageously in the form of flakes or spherical particles or oval particles. They can in particular be obtained by chemical reduction of a gold salt or by atomization.

Les paillettes d'or correspondent à des particules d'or essentiellement bidimensionnelles.Gold flakes correspond to essentially two-dimensional gold particles.

De manière avantageuse, les particules d'or présentent une granulométrie micrométrique.Advantageously, the gold particles have a micrometric particle size.

Les particules d'or, avantageusement les poudres de paillettes d'or, présentent une surface spécifique avantageusement comprise entre 0,22 m2/g et 0,35 m2/g, plus avantageusement entre 0,26 m2/g et 0,28 m2/g.The gold particles, advantageously the powders of gold flakes, have a specific surface advantageously comprised between 0.22 m 2 /g and 0.35 m 2 /g, more advantageously between 0.26 m 2 /g and 0 .28 m 2 /g.

Les particules, avantageusement sphériques ou parallélépipédiques ou cylindriques ou ovales, présentent une taille moyenne avantageusement comprise entre 1 µm et 60 µm, plus avantageusement entre 1 µm et 50 µm. Par taille, on désigne la dimension la plus importante des particules, la longueur pour des particules ovales ou le diamètre pour des particules sphériques.The particles, advantageously spherical or parallelepipedal or cylindrical or oval, have an average size advantageously comprised between 1 μm and 60 μm, more advantageously between 1 μm and 50 μm. By size is meant the largest dimension of the particles, the length for oval particles or the diameter for spherical particles.

Les paillettes ont une taille moyenne avantageusement inférieure ou égale à 650 micromètres (≤ 650 µm), plus avantageusement entre 1 micromètre et 3 micromètres. Par taille, on désigne la dimension la plus importante des paillettes, par exemple la longueur.The flakes have an average size advantageously less than or equal to 650 micrometers (≤ 650 μm), more advantageously between 1 micrometer and 3 micrometers. By size, we designate the most important dimension of the sequins, for example the length.

La distribution de taille des particules d'or est avantageusement relativement étroite. De manière générale, la taille des particules varie de moins de 25 %, avantageusement de moins de 15 %, plus avantageusement de moins de 10 %, par rapport à la taille moyenne des particules. Ces pourcentages correspondent à l'écart de taille maximum entre les plus grandes particules et les plus petites particules d'or de la composition composite.The size distribution of the gold particles is advantageously relatively narrow. Generally, the particle size varies by less than 25%, preferably less than 15%, more preferably less than 10%, relative to the average particle size. These percentages correspond to the maximum difference in size between the largest particles and the smallest particles of gold in the composite composition.

A titre d'exemple, les particules d'or de forme sphérique présentent une distribution d50 égale à 21,34 µm et d90 égale à 34,48 µm. De manière avantageuse, 50 %, en poids, des particules sphériques présentent donc une taille inférieure à 21,34 µm alors que 90 %, en poids, des particules sphériques présentent une taille inférieure à 34,48 µm.By way of example, the spherical gold particles have a distribution d50 equal to 21.34 μm and d90 equal to 34.48 μm. Advantageously, 50%, by weight, of the spherical particles therefore have a size of less than 21.34 μm while 90%, by weight, of the spherical particles have a size of less than 34.48 μm.

L'utilisation de particules de taille supérieure à 600 nm permet de maintenir les propriétés de conduction (thermique et électrique) de l'or au sein du matériau composite et ce, même lorsque les particules d'or représentent 75,00 % en poids du matériau composite.The use of particles larger than 600 nm makes it possible to maintain the conduction properties (thermal and electrical) of gold within the composite material, even when the gold particles represent 75.00% by weight of the composite material.

En revanche, l'utilisation de particules ayant une taille inférieure à 600 nm génère une poudre ayant une surface spécifique trop importante, ce qui nécessite l'ajout d'une quantité plus importante de résine pour maintenir une coulabilité permettant la mise en forme de la composition composite. En effet, les particules de taille inférieure à 600 nm ne permettent pas d'obtenir une composition composite contenant au moins 75 % en poids de particules d'or et présentant des propriétés satisfaisantes. Il en résulte des propriétés mécaniques du matériau composite nettement inférieures à celles du matériau composite selon l'invention.On the other hand, the use of particles having a size of less than 600 nm generates a powder having too large a specific surface, which requires the addition of a larger quantity of resin to maintain a flowability allowing the shaping of the composite composition. Indeed, particles with a size of less than 600 nm do not make it possible to obtain a composite composition containing at least 75% by weight of gold particles and having satisfactory properties. This results in mechanical properties of the composite material that are markedly lower than those of the composite material according to the invention.

Les particules d'or ayant une taille supérieure à 600 nm, notamment sous la forme de paillettes d'or, présentent l'avantage de permettre la percolation des particules d'or et donc la conduction électrique. Ceci est notamment dû au facteur de forme des particules qui, lorsqu'il augmente, engendre la diminution du seuil de percolation et donc une diminution de la quantité de particules nécessaire. Ce phénomène est encore plus présent lorsque les particules d'or sont sous la forme de paillettes, en raison de leur forme plate et de leur distribution de taille étroite.Gold particles having a size greater than 600 nm, in particular in the form of gold flakes, have the advantage of allowing percolation of gold particles and therefore electrical conduction. This is in particular due to the form factor of the particles which, when it increases, causes the reduction of the percolation threshold and therefore a reduction in the quantity of particles required. This phenomenon is even more present when the gold particles are in the form of flakes, due to their flat shape and narrow size distribution.

Particules de nitrure de titaneTitanium nitride particles

Les particules de nitrure de titane (TiN) sont des charges conductrices d'électricité.Titanium Nitride (TiN) particles are electrically conductive fillers.

Du fait de cette conductivité, une portion de la poudre d'or peut être remplacée par la poudre de nitrure de titane afin d'avoir, dans la composition finale, une proportion d'or supérieure ou égale à 75 % massique d'or et afin de garder la conductivité électrique du matériau ainsi formé. Sans la présence d'une autre charge conductrice, en l'occurrence les particules de TiN, une proportion de 90 % massique d'or dans le matériau final pourrait être nécessaire pour que celui-ci soit conducteur électrique.Because of this conductivity, a portion of the gold powder can be replaced by titanium nitride powder in order to have, in the final composition, a proportion of gold greater than or equal to 75% by mass of gold and in order to keep the electrical conductivity of the material thus formed. Without the presence of another conductive filler, in this case the TiN particles, a proportion of 90% by mass of gold in the final material could be necessary for it to be electrically conductive.

Elles représentent entre 2,00 % et 10,00 % par rapport au poids de la composition composite (ou du matériau composite), plus avantageusement 6,00 % à 10,00 %, encore plus avantageusement 8,00 % à 9,00 %.They represent between 2.00% and 10.00% relative to the weight of the composite composition (or of the composite material), more advantageously 6.00% to 10.00%, even more advantageously 8.00% to 9.00 %.

Le nitrure de titane présente l'avantage d'avoir une couleur dorée, identique ou proche de celle de l'or. La poudre de nitrure de titane a en revanche une couleur un peu plus verte que la poudre d'or. En outre, le nitrure de titane est une céramique. A ce titre, le nitrure de titane apporte des propriétés de dureté au matériau composite, tout en présentant une faible masse volumique, de l'ordre de 5,24 g.cm-3.Titanium nitride has the advantage of having a golden color, identical or close to that of gold. Titanium nitride powder, on the other hand, has a slightly greener color than gold powder. Also, titanium nitride is a ceramic. As such, titanium nitride provides hardness properties to the composite material, while having a low density, of the order of 5.24 g.cm −3 .

Les particules de nitrure de titane peuvent se présenter avantageusement sous la forme de poudre.The titanium nitride particles can advantageously be in powder form.

Leur taille moyenne est avantageusement comprise entre 0,10 µm et 3,00 µm, plus avantageusement entre 1,00 µm et 3,00 µm. La taille d'une particule correspond à la dimension la plus importante de la section d'une particule (vue en coupe), par exemple le diamètre pour des particules sphériques.Their average size is advantageously between 0.10 μm and 3.00 μm, more advantageously between 1.00 μm and 3.00 μm. The size of a particle corresponds to the most important dimension of the section of a particle (sectional view), for example the diameter for spherical particles.

Résine époxyEpoxy resin

Comme déjà indiqué, la résine époxy durcit par polymérisation de monomères et/ou de pré-polymères et/ou par réticulation en présence d'un durcisseur.As already indicated, the epoxy resin hardens by polymerization of monomers and/or prepolymers and/or by crosslinking in the presence of a hardener.

De manière générale, la résine époxy est incolore après durcissement. En d'autres termes, elle ne modifie pas la couleur des particules d'or.Generally speaking, epoxy resin is colorless after curing. In other words, it does not modify the color of the gold particles.

Elle présente une masse volumique avantageusement comprise entre 0,9 et 1,4 g.cm-3.It has a density advantageously between 0.9 and 1.4 g.cm -3 .

La composition composite (ou le matériau composite) comprend entre 5 % et 15 % de résine époxy et de durcisseur (résine + durcisseur = 5 % à 15 %), par rapport au poids de la composition composite, plus avantageusement entre 10 % et 15 % et encore plus avantageusement entre 12 % et 13 %.The composite composition (or the composite material) comprises between 5% and 15% of epoxy resin and hardener (resin + hardener = 5% to 15%), relative to the weight of the composite composition, more advantageously between 10% and 15 % and even more advantageously between 12% and 13%.

La résine époxy est avantageusement le poly(bisphénol A-co-épichlorohydrine), plus avantageusement le composé chimique ayant pour numéro CAS 25068-38-6.The epoxy resin is advantageously poly(bisphenol A-co-epichlorohydrin), more advantageously the chemical compound having CAS number 25068-38-6.

Après durcissement, la résine époxy est avantageusement du poly(bisphénol A-co-épichlorohydrine) réticulé.After curing, the epoxy resin is advantageously crosslinked poly(bisphenol A-co-epichlorohydrin).

A titre d'exemple, la résine époxy peut être :

  • un mélange de poly(bisphénol A-co-épichlorohydrine), d'alcool benzylique (CAS 100-51-6), d'acide benzoïque 4-((méthylphénylamino)méthylène)amino)- éthyl ester (CAS 57834-33-0) et d'alkyl (C12-C14) glycidyl éther (CAS 68609-97-2) ; ou
  • un mélange de poly(bisphénol A-co-épichlorohydrine), de propanetriol-1,2,3,oxydes de glycidyle (CAS 90529-77-4) de formaldehyde polymérisé avec le (chlorométhyl)oxirane et le phénol (CAS 9003-36-5) ayant un poids moléculaire moyen en nombre Mn avantageusement inférieur ou égal à 700 g/mol et de 1,4-bis(2,3-époxypropoxy)butane (CAS 2425-79-8).
By way of example, the epoxy resin can be:
  • a mixture of poly(bisphenol A-co-epichlorohydrin), benzyl alcohol (CAS 100-51-6), benzoic acid 4-((methylphenylamino)methylene)amino)-ethyl ester (CAS 57834-33-0 ) and alkyl (C12-C14) glycidyl ether (CAS 68609-97-2); Where
  • a mixture of poly(bisphenol A-co-epichlorohydrin), propanetriol-1,2,3,glycidyl oxides (CAS 90529-77-4) formaldehyde polymerized with (chloromethyl)oxirane and phenol (CAS 9003-36 -5) having a number-average molecular weight Mn advantageously less than or equal to 700 g/mol and of 1,4-bis(2,3-epoxypropoxy)butane (CAS 2425-79-8).

La résine époxy peut notamment correspondre à une formulation commercialisée sous le nom Super Sap® CCR Epoxy Resin (de chez Entropy Resin), EPIKOTE™ Resin MGS LR 385 (de chez Hexion) ou EPIKOTE™ Resin MGS L 235 (de chez Hexion).The epoxy resin may in particular correspond to a formulation marketed under the name Super Sap® CCR Epoxy Resin (from Entropy Resin), EPIKOTE ™ Resin MGS LR 385 (from Hexion) or EPIKOTE ™ Resin MGS L 235 (from Hexion).

Fibresfibers

Les fibres sont des fibres en matériau conducteur électrique, plus avantageusement des fibres de carbone, notamment des microfibres de carbone.The fibers are fibers made of an electrically conductive material, more advantageously carbon fibers, in particular carbon microfibers.

Elles permettent d'améliorer la résistance à la traction du matériau composite.They make it possible to improve the tensile strength of the composite material.

Les fibres de carbone étant compatibles avec les différents constituants du matériau composite, elles sont aisément intégrées au sein de la composition composite ou du matériau composite.Since the carbon fibers are compatible with the various constituents of the composite material, they are easily integrated within the composite composition or the composite material.

Les fibres représentent entre 0,5 % et 6,0 % en poids de la composition composite (ou du matériau composite), plus avantageusement 1,0 % et 4,0 % en poids.The fibers represent between 0.5% and 6.0% by weight of the composite composition (or composite material), more preferably 1.0% and 4.0% by weight.

Elles présentent une longueur moyenne avantageusement comprise entre 100 micromètres et 500 micromètres, plus avantageusement entre 200 micromètres et 250 micromètres.They have an average length advantageously between 100 micrometers and 500 micrometers, more advantageously between 200 micrometers and 250 micrometers.

Selon un mode de réalisation particulier, les fibres présentent une longueur moyenne de l'ordre de 220 micromètres.According to a particular embodiment, the fibers have an average length of the order of 220 micrometers.

DurcisseurHardener

Comme déjà indiqué, la composition composite peut également comprendre un durcisseur.As already indicated, the composite composition can also comprise a hardener.

La composition composite (ou le matériau composite) comprend entre 10 % et 15 % de résine époxy et de durcisseur (résine + durcisseur = 10 % à 15 %), par rapport au poids de la composition composite, plus avantageusement entre 12 % et 13 %.The composite composition (or the composite material) comprises between 10% and 15% of epoxy resin and hardener (resin+hardener=10% to 15%), relative to the weight of the composite composition, more advantageously between 12% and 13%.

L'homme du métier saura ajuster la quantité de durcisseur en fonction de la quantité de résine époxy. Néanmoins, le matériau composite présente un rapport, en poids, résine époxy/durcisseur avantageusement compris entre 100/30 et 100/50, plus avantageusement entre 100/35 et 100/43.A person skilled in the art will know how to adjust the quantity of hardener according to the quantity of epoxy resin. Nevertheless, the composite material has a ratio, by weight, epoxy resin/hardener advantageously comprised between 100/30 and 100/50, more advantageously between 100/35 and 100/43.

Le durcisseur peut être une polyamine, avantageusement une diamine, de préférence le polyoxypropylènediamine, avantageusement le composé chimique ayant pour numéro CAS 9046-10-0.The hardener may be a polyamine, advantageously a diamine, preferably polyoxypropylenediamine, advantageously the chemical compound having CAS number 9046-10-0.

Selon un autre mode de réalisation, le durcisseur peut être un mélange choisi dans le groupe comprenant :

  • un mélange de polyoxypropylènediamine et de 1-piperazine éthanamine (CAS 140-31-8) ;
  • un mélange de 3-aminométhyl-3,5,5-triméthylcyclohexylamine (CAS 2855-13-2), d'alcool benzylique (CAS 100-51-6), de polymère de phénol, 4,4'-(1-méthylèthylidène) bis- avec 5-amino-1,3,3-triméthylcyclohexaneméthanamine et (chlorométhyl)oxirane (CAS 38294-64-3), d'acide salicylique (CAS 69-72-7) et de nonylphénol (CAS 25154-52-3) ; et
  • un mélange de 3-aminométhyl-3,5,5-triméthylcyclohexylamine (CAS 2855-13-2), de triméthylolpropane poly (oxypropylène) triamine (CAS 39423-51-3) et de 2,2'-diméthyl-4,4'méthylènebis (cyclohexylamine) (CAS 6864-37-5).
According to another embodiment, the hardener can be a mixture chosen from the group comprising:
  • a mixture of polyoxypropylenediamine and 1-piperazine ethanamine (CAS 140-31-8);
  • a mixture of 3-aminomethyl-3,5,5-trimethylcyclohexylamine (CAS 2855-13-2), benzyl alcohol (CAS 100-51-6), phenol polymer, 4,4'-(1-methylethylidene ) bis- with 5-amino-1,3,3-trimethylcyclohexanemethanamine and (chloromethyl)oxirane (CAS 38294-64-3), salicylic acid (CAS 69-72-7) and nonylphenol (CAS 25154-52- 3); and
  • a mixture of 3-aminomethyl-3,5,5-trimethylcyclohexylamine (CAS 2855-13-2), trimethylolpropane poly (oxypropylene) triamine (CAS 39423-51-3) and 2,2'-dimethyl-4,4 'methylenebis (cyclohexylamine) (CAS 6864-37-5).

Le durcisseur peut notamment correspondre à une formulation commercialisée sous le nom Super Sap® CCS Hardener (de chez Entropy Resin), Super Sap® CCF Hardener (de chez Entropy Resin), EPIKURE™ MGS LH 385 (de chez Hexion), EPIKURE™ MGS LH 386 (de chez Hexion) ou EPIKURE™ MGS LH 238 (de chez Hexion).The hardener may in particular correspond to a formulation marketed under the name Super Sap ® CCS Hardener (from Entropy Resin), Super Sap ® CCF Hardener (from Entropy Resin), EPIKURE ™ MGS LH 385 (from Hexion), EPIKURE ™ MGS LH 386 (from Hexion) or EPIKURE ™ MGS LH 238 (from Hexion).

Matériau compositeComposite material

Le matériau composite selon l'invention est homogène. En d'autres termes, ses composants sont répartis de manière régulière au sein du matériau composite. Ainsi, le matériau composite ne comprend pas de gradient de concentration de ses composants. Il présente une masse volumique avantageusement comprise entre 4,00 g.cm-3 et 7,00 g.cm-3, plus avantageusement entre 5,00 g.cm-3 et 6,00 g.cm-3 ; la masse volumique de l'or étant égale à 19,30 g.cm-3.The composite material according to the invention is homogeneous. In other words, its components are evenly distributed within the composite material. Thus, the composite material does not include a concentration gradient of its components. It has a density advantageously between 4.00 g.cm -3 and 7.00 g.cm -3 , more advantageously between 5.00 g.cm -3 and 6.00 g.cm -3 ; the density of gold being equal to 19.30 g.cm -3 .

Le matériau composite se présente sous la forme d'un solide. Comme déjà indiqué, il comprend une matrice polymère formée par la résine époxy et le durcisseur, c'est-à-dire un réseau tridimensionnel résultant de la polymérisation et/ou de la réticulation de la résine époxy en présence du durcisseur.The composite material is in the form of a solid. As already indicated, it comprises a polymer matrix formed by the epoxy resin and the hardener, that is to say a three-dimensional network resulting from the polymerization and/or the crosslinking of the epoxy resin in the presence of the hardener.

Le matériau composite est avantageusement constitué de particules d'or, de particules de nitrure de titane, de fibres et de la matrice polymère formée par la résine époxy et par le durcisseur. Plus précisément, les différents constituants du matériau composite sont répartis de manière homogène au sein de la matrice polymère.The composite material advantageously consists of gold particles, titanium nitride particles, fibers and the polymer matrix formed by the epoxy resin and by the hardener. More specifically, the various constituents of the composite material are distributed homogeneously within the polymer matrix.

Il peut se présenter sous la forme d'un objet fini ou d'une préforme. Ainsi, lorsqu'il a été mis en forme préalablement au durcissement de la résine, il s'agit d'un article fini. Il peut également se présenter sous la forme d'une préforme qui peut être usinée, par exemple un cylindre ou un parallélépipède, notamment un pavé.It can be in the form of a finished object or a preform. Thus, when it has been shaped prior to the hardening of the resin, it is a finished article. It can also be in the form of a preform which can be machined, for example a cylinder or a parallelepiped, in particular a block.

Comme déjà indiqué, le matériau composite selon l'invention est conducteur électrique.As already indicated, the composite material according to the invention is electrically conductive.

Procédé de fabrication du matériau compositeComposite material manufacturing process

La présente invention concerne également un procédé de fabrication d'un matériau composite comprenant les étapes suivantes :

  1. a) préparation d'une composition composite comprenant, en poids :
    • au moins 75,00 % en poids de particules d'or,
    • 2% à 10% des particules de nitrure de titane,
    • 5% à 15% une résine époxy, et
    • des fibres,
      • 0,5% à 6,0% les particules d'or ayant une taille supérieure à 600 nm,
  2. b) addition d'un durcisseur dans la composition composite,
  3. c) mise en forme de cette composition composite et durcissement de la résine époxy pour former un matériau composite.
The present invention also relates to a process for manufacturing a composite material comprising the following steps:
  1. a) preparation of a composite composition comprising, by weight:
    • at least 75.00% by weight of gold particles,
    • 2% to 10% titanium nitride particles,
    • 5% to 15% an epoxy resin, and
    • fibers,
      • 0.5% to 6.0% gold particles having a size greater than 600 nm,
  2. b) addition of a hardener in the composite composition,
  3. c) shaping this composite composition and curing the epoxy resin to form a composite material.

La nature de la composition composite de l'étape a) (sans durcisseur) ou de l'étape b) (avec durcisseur) est identique à celle de la composition composite ou du matériau composite décrits ci-dessus.The nature of the composite composition of step a) (without hardener) or of step b) (with hardener) is identical to that of the composite composition or of the composite material described above.

Etape a)Step a)

De manière générale, de l'or sous forme de paillettes ou de particules, des particules de nitrure de titane, de la résine époxy et des fibres sont mélangées préalablement à l'addition d'un durcisseur. Toutefois, selon un autre mode de réalisation, les étapes a) et b) peuvent être réalisées par addition simultanée de tous les composants du matériau composite.In general, gold in the form of flakes or particles, particles of titanium nitride, epoxy resin and fibers are mixed before adding a hardener. However, according to another embodiment, steps a) and b) can be carried out by simultaneous addition of all the components of the composite material.

La composition composite issue de l'étape a) se présente généralement sous la forme d'une pâte.The composite composition resulting from step a) is generally in the form of a paste.

Entre les étapes a) et b), cette composition composite peut être homogénéisée par passage dans un broyeur, avantageusement un broyeur tricylindre, également appelé laminoir trois cylindres.Between steps a) and b), this composite composition can be homogenized by passing it through a mill, advantageously a three-roll mill, also called a three-roll mill.

Le passage dans ce type de broyeur permet non seulement d'homogénéiser la composition composite mais aussi de casser les éventuels agrégats formés par les différents composants de la composition composite. L'homogénéité de la composition composite est un critère important pour permettre, ultérieurement, la percolation des particules conductrices entre elles dans le matériau composite.Passage through this type of grinder makes it possible not only to homogenize the composite composition but also to break up any aggregates formed by the various components of the composite composition. The homogeneity of the composite composition is an important criterion for subsequently allowing the percolation of the conductive particles between them in the composite material.

La formation de la composition composite, avec ou sans durcisseur, engendre généralement l'incorporation de bulles d'air dans la pâte.The formation of the composite composition, with or without a hardener, generally causes the incorporation of air bubbles into the paste.

Aussi, afin d'éliminer ces bulles d'air, le procédé peut comprendre une étape d'élimination de gaz. Cette étape peut être avantageusement réalisée au moyen d'une centrifugeuse ou d'une centrifugeuse/mélangeur planétaire avec un vide partiel. Elle peut être réalisée préalablement à l'étape b) et/ou préalablement à l'étape c) et/ou simultanément à l'étape c).Also, in order to eliminate these air bubbles, the method can comprise a gas elimination step. This step can advantageously be carried out using a centrifuge or a planetary centrifuge/mixer with a partial vacuum. It can be carried out before step b) and/or before step c) and/or simultaneously with step c).

La préparation de la composition composite (étape a) et/ou b)) et les éventuels traitements (homogénéisation et élimination de l'air) sont avantageusement réalisés à une température comprise entre 20°C et 25°C. Toutefois, la température peut varier d'une étape à l'autre.The preparation of the composite composition (step a) and/or b)) and any treatments (homogenization and elimination of air) are advantageously carried out at a temperature of between 20°C and 25°C. However, the temperature may vary from step to step.

Etape b)Step b)

L'étape b) consiste à introduire au moins un durcisseur de la résine époxy. Comme déjà indiqué, ce durcisseur permet la polymérisation et/ou la réticulation de la résine époxy.Step b) consists in introducing at least one epoxy resin hardener. As already indicated, this hardener allows the polymerization and/or crosslinking of the epoxy resin.

Après l'addition du durcisseur (entre les étapes b) et c)), la composition composite peut être homogénéisée par un mélangeur à hélice ou un passage dans un broyeur, avantageusement un broyeur tricylindre également appelé laminoir trois cylindres.After the addition of the hardener (between steps b) and c)), the composite composition can be homogenized by a propeller mixer or passage through a mill, advantageously a three-roll mill also called a three-roll mill.

Etape c)Step c)

Une fois la composition composite de l'étape b) obtenue, elle peut être mise en forme.Once the composite composition of step b) has been obtained, it can be shaped.

La mise en forme est réalisée selon les techniques conventionnelles, par exemple dans un moule. Il peut s'agir d'un moule permettant d'obtenir un article fini ou une préforme qui sera ultérieurement usinée.The shaping is carried out according to conventional techniques, for example in a mould. It may be a mold making it possible to obtain a finished article or a preform which will subsequently be machined.

Selon un mode de réalisation particulier, le moule est placé dans une centrifugeuse, assurant ainsi de manière simultanée l'élimination d'air et la mise en forme du matériau composite.According to a particular embodiment, the mold is placed in a centrifuge, thus simultaneously ensuring the elimination of air and the shaping of the composite material.

La vitesse de centrifugation peut être ajustée en fonction de la viscosité de la composition composite, par exemple de l'ordre de 2000 G pendant une heure (1 G = 9,80665 m.s-2).The centrifugation speed can be adjusted according to the viscosity of the composite composition, for example of the order of 2000 G for one hour (1 G=9.80665 ms -2 ).

La centrifugation est avantageusement réalisée à une température comprise entre 20°C et 50°C, plus avantageusement entre 25°C et 35°C.The centrifugation is advantageously carried out at a temperature between 20°C and 50°C, more advantageously between 25°C and 35°C.

L'augmentation de la température permet de fluidifier la composition composite et accélère le durcissement de la résine époxy.The increase in temperature makes it possible to fluidify the composite composition and accelerates the hardening of the epoxy resin.

Ainsi, dans le but d'éliminer un maximum d'air, la composition composite peut être centrifugée avant et/ou après l'étape b), c'est-à-dire avant et/ou après l'addition du durcisseur.Thus, with the aim of eliminating as much air as possible, the composite composition can be centrifuged before and/or after step b), that is to say before and/or after the addition of the hardener.

L'homogénéisation permet d'assurer l'homogénéité de microstructure du matériau composite à l'état durci.Homogenization makes it possible to ensure the homogeneity of the microstructure of the composite material in the hardened state.

Le durcissement est, au moins partiellement, réalisé simultanément à la mise en forme. En effet, un pré-durcissement peut être réalise lors de la mise en forme. Le pré-durcissement permet de manipuler et de terminer le durcissement du matériau composite en dehors du moule de mise en forme.Hardening is, at least partially, carried out simultaneously with shaping. Indeed, a pre-hardening can be carried out during shaping. Pre-curing allows manipulation and completion of the curing of the composite material outside the shaping mold.

Une autre méthode consiste à utiliser un mélangeur planétaire, avantageusement avec un vide partiel pour dégazer la composition composite se présentant sous la forme d'une pâte. Cette étape de mélange est avantageusement suivie d'une étape de mise en forme dans un moule par gravité ou par centrifugation légère (par exemple à 250 G pendant 10 min; 1 G = 9,80665 m·s-2).Another method consists in using a planetary mixer, advantageously with a partial vacuum to degas the composite composition which is in the form of a paste. This mixing step is advantageously followed by a shaping step in a mold by gravity or by light centrifugation (for example at 250 G for 10 min; 1 G=9.80665 m·s −2 ).

Comme déjà mentionné, le durcissement correspond à la formation d'une matrice polymère par réaction entre la résine époxy et le durcisseur.As already mentioned, the hardening corresponds to the formation of a matrix polymer by reaction between the epoxy resin and the hardener.

Le durcissement de l'étape c) est avantageusement réalisé à une température comprise entre 20°C et 30°C, plus avantageusement entre 25°C et 30°C. Dans ces conditions, les particules de nitrure de titane ne sont pas céramisées.The hardening of step c) is advantageously carried out at a temperature between 20°C and 30°C, more advantageously between 25°C and 30°C. Under these conditions, the titanium nitride particles are not ceramized.

Il est avantageusement réalisé pendant une durée comprise entre 15 minutes et 48 heures, plus avantageusement entre 1 heure et 24 heures.It is advantageously carried out for a period of between 15 minutes and 48 hours, more advantageously between 1 hour and 24 hours.

Article comprenant le matériau compositeArticle comprising the composite material

La présente invention concerne également un matériau composite mis en forme ou d'une préforme pouvant être usinée avant de former un objet fini.The present invention also relates to a shaped composite material or a preform that can be machined before forming a finished object.

Elle concerne en outre un article d'horlogerie, de bijouterie ou de joaillerie comprenant le matériau composite ayant été durci. Il peut s'agir de bracelets, de boucles d'oreilles, de pendentifs, de colliers, de broches, d'épingles à cravate, d'épingles à cheveux, de boucles de ceinture, de boutons, de boutons de manchette, de boucles de ceinture, de boitiers de montre...It also relates to an article of watchmaking, jewelery or jewelery comprising the composite material having been hardened. It can be bracelets, earrings, pendants, necklaces, brooches, tie pins, hairpins, belt buckles, buttons, cufflinks, buckles belts, watch cases...

L'invention et les avantages qui en découlent ressortiront mieux de l'exemple suivant donné afin d'illustrer l'invention et non de manière limitative.The invention and the resulting advantages will emerge better from the following example given in order to illustrate the invention and not in a limiting manner.

EXEMPLES DE REALISATION DE L'INVENTIONEXAMPLES OF REALIZATION OF THE INVENTION

Un matériau composite selon l'invention a été préparé selon le mode opératoire suivant :

  • a)-b) préparation d'une composition composite comprenant, en poids :
    • 75,00 % de particules d'or,
    • 8,45 % de particules de nitrure de titane,
    • 4,00 % de microfibres de carbone,
    • 12,55 % de résine époxy (EPIKOTE™ Resin MGS L 235) et d'un durcisseur (EPIKURE™ MGS LH 238) dans un rapport, en poids, résine/durcisseur de 100/35,
  • c) mise en forme de cette composition composite et durcissement de la résine entre 20°C et 25°C pendant 24 heures à 7 jours.
A composite material according to the invention was prepared according to the following procedure:
  • a)-b) preparation of a composite composition comprising, by weight:
    • 75.00% gold particles,
    • 8.45% titanium nitride particles,
    • 4.00% carbon microfibers,
    • 12.55% of epoxy resin (EPIKOTE ™ Resin MGS L 235) and a hardener (EPIKURE ™ MGS LH 238) in a ratio, by weight, resin/hardener of 100/35,
  • c) shaping of this composite composition and hardening of the resin between 20° C. and 25° C. for 24 hours to 7 days.

Les particules d'or sont des paillettes présentant une taille moyenne de l'ordre de 5,5 µm.The gold particles are flakes having an average size of the order of 5.5 μm.

Les particules de nitrure de titane présentent une taille moyenne entre 0,10 micromètre et 3,00 micromètres.The titanium nitride particles have an average size between 0.10 micrometers and 3.00 micrometers.

Les micro fibres de carbone présentent une longueur moyenne entre 100 micromètres et 500 micromètres.The micro carbon fibers have an average length between 100 micrometers and 500 micrometers.

Le tableau 1 ci-dessous récapitule les données relatives à ce matériau composite dont la masse volumique théorique est de 5,5 g.cm-3. Tableau 1 : matériau composite selon l'invention Paillettes d'or Nitrure de titane Microfibres de carbone Résine époxy + durcisseur Masse volumique (g.cm-3) 19,30 5,24 2,25 1,15 Pourcentage en poids 75,00 8,45 4,00 12,55 Pourcentage volumique 21,36 8,87 9,77 60,00 Table 1 below summarizes the data relating to this composite material, the theoretical density of which is 5.5 g.cm -3 . Table 1: composite material according to the invention gold glitter titanium nitride Carbon microfibers Epoxy resin + hardener Density (g.cm -3 ) 19.30 5.24 2.25 1.15 Percentage by weight 75.00 8.45 4.00 12.55 Volume percentage 21.36 8.87 9.77 60.00

Ce matériau étant conducteur électrique, il peut ensuite être recouvert d'un plaquage.This material being electrically conductive, it can then be covered with a plating.

Claims (15)

  1. A composite composition comprising, by weight with respect to the weight of the composite composition:
    - at least 75.00% of gold particles,
    - 2% to 10% of titanium nitride particles,
    - 5% to 15% of an epoxy resin,
    - 0.5% to 6.0% of fibres of an electrically conductive material, the gold particles being more than 600 nm in size.
  2. The composite composition as claimed in claim 1, characterized in that the composite composition comprises between 75.00% and 92.00% of gold particles.
  3. The composite composition as claimed in claim 1 or claim 2, characterized in that the composite composition comprises between 2% and 10%, advantageously between 6% and 10%, more advantageously between 8.00% and 9.00% of titanium nitride particles.
  4. The composite composition as claimed in one of claims 1 to 3, characterized in that the epoxy resin comprises poly(bisphenol A-co-epichlorohydrin), advantageously the chemical compound with CAS number 25068-38-6.
  5. The composite composition as claimed in one of claims 1 to 4, characterized in that the fibres are carbon microfibres, advantageously carbon microfibres with an average length comprised between 100 micrometres and 500 micrometres, more advantageously between 200 micrometres and 250 micrometres.
  6. The composite composition as claimed in one of claims 1 to 5, characterized in that the composite composition comprises a curing agent.
  7. The composite composition as claimed in one of claims 1 to 6, characterized in that the composite composition comprises a curing agent, the curing agent being a polyamine, advantageously a diamine, more advantageously polyoxypropylene diamine.
  8. The composite composition as claimed in one of claims 1 to 7, characterized in that the composite composition comprises a curing agent and has an epoxy resin/curing agent weight ratio comprised between 100/30 and 100/50, advantageously between 100/35 and 100/43.
  9. The composite composition as claimed in one of claims 1 to 8, characterized in that the composite composition comprises between 5% and 15% of epoxy resin and of curing agent, advantageously between 10% and 15%, more advantageously between 12% and 13%.
  10. The composite material constituted by the composite composition as claimed in one of claims 6 to 9, the epoxy resin and the curing agent forming a polymer matrix.
  11. A timepiece or jewellery article comprising the composite material as claimed in claim 10.
  12. A method for manufacturing a composite material, comprising the following steps:
    a) preparing a composite composition comprising, by weight:
    - at least 75.00% of gold particles,
    - 2% to 10% of titanium nitride particles,
    - 5% to 15% of an epoxy resin,
    - 0.5% to 6.0% of fibres of an electrically conductive material, the gold particles being more than 600 nm in size,
    b) adding a curing agent to the composite composition,
    c) shaping the composite composition and curing the epoxy resin to form a composite material.
  13. The method as claimed in claim 12, characterized in that it comprises a step for eliminating gas, this step advantageously being carried out by means of a centrifuge or a planetary mixer with a partial vacuum prior to step b) and/or prior to step c) and/or simultaneously with step c).
  14. The method as claimed in claim 12 or claim 13, characterized in that it comprises a step for homogenization by passage through a three-cylinder mill, this step being carried out between step a) and step b) and/or between step b) and step c).
  15. The method as claimed in one of claims 12 to 14, characterized in that the curing of step c) is carried out for a period comprised between 15 minutes and 48 hours, advantageously at a temperature comprised between 25°C and 30°C.
EP19185638.4A 2019-07-11 2019-07-11 Composite material made of gold Active EP3763842B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
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Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP19185638.4A EP3763842B1 (en) 2019-07-11 2019-07-11 Composite material made of gold

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EP3763842B1 true EP3763842B1 (en) 2022-09-07

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Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1599399A (en) 1977-05-13 1981-09-30 Johnson Matthey Co Ltd Production of metallic articles
DE602007001180D1 (en) 2007-04-13 2009-07-09 Lorenzo Brunetti A method for producing an alloy for decorative articles and alloy for decorative articles, which can be produced in particular by this method
EP2305756A1 (en) 2009-09-22 2011-04-06 Rolex Sa Coloured composite material containing nanoparticles
US20120164429A1 (en) * 2009-12-01 2012-06-28 Applied Nanostructured Solutions, Llc Metal matrix composite materials containing carbon nanotube-infused fiber materials and methods for production thereof
CH704429B1 (en) 2011-01-26 2016-03-31 Ecometal Sa Composite material for the production of ornamental articles and procedure for the production of an ornamental article.
EP2683841B1 (en) 2011-03-08 2019-10-30 Hublot Sa Composite material comprising a precious metal, manufacturing process and use of such a material
TWM532467U (en) * 2013-06-10 2016-11-21 蘋果公司 A housing for an electronic device

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